Morphology Driven by Molecular Structure of Thiazole-Based Polymers for Use in Field-Effect Transistors and Solar Cells.

The effects of the molecular structure of thiazole-based polymers on the active layer morphologies and performances of electronic and photovoltaic devices were studied. Thus, thiazole-based conjugated polymers with a novel thiazole-vinylene-thiazole (TzVTz) structure were designed and synthesized. The TzVTz structure was introduced to extend the π conjugation and coplanarity of the polymer chains. By combining alkylthienyl-substituted benzo[1,2-b:4,5-b']dithiophene (BDT) or dithieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene (DTBDT) electron-donating units and a TzVTz electron-accepting unit, enhanced intermolecular interactions and charge transport were obtained in the novel polymers BDT-TzVTz and DTBDT-TzVTz. With a view to using the polymers in transistor and photovoltaic applications, the molecular self-assembly in and their nanoscale morphologies of the active layers were controlled by thermal annealing to enhance the molecular packing and by introducing a diphenyl ether solvent additive to improve the miscibility between polymer donors and [6,6]phenyl-C71-butyric acid methyl ester (PC71 BM) acceptors, respectively. The morphological characterization of the photoactive layers showed that a higher degree of π-electron delocalization and more favorable molecular packing in DTBDT-TzVTz compared with in BDT-TzVTz leads to distinctly higher performances in transistor and photovoltaic devices. The superior performance of a photovoltaic device incorporating DTBDT-TzVTz was achieved through the superior miscibility of DTBDT-TzVTz with PC71 BM and the improved crystallinity of DTBDT-TzVTz in the nanofibrillar structure.

Acene-Modified Small-Molecule Donors for Organic Photovoltaics.

A series of acene-modified small molecules have been designed and synthesized, and their photovoltaic characteristics were studied by using the small molecules in organic photovoltaics (OPVs). Different cores were introduced to modulate the conjugation lengths of the small molecules and the bulk heterojunction (BHJ) morphologies. Three small-molecule donors were prepared, namely Ph-TTR, Na-TTR, and An-TTR, which have phenyl, naphthalene, and anthracene moieties, respectively, as conjugated cores. These donors were synthesized in a few steps and exhibited favorable BHJ morphologies, thereby giving promising power conversion efficiencies (PCEs). The donors showed excellent miscibility with the acceptor PC71 BM, and the use of the additive 1,8-diiodooctane (DIO) led to a remarkable increase in crystallinity, thereby increasing the PCEs of their OPVs. Of the three donors, Na-TTR showed the most efficient charge carrier generation and favorable molecular packing structures; hence, of the three types of devices tested, the Na-TTR:PC71 BM devices exhibited the highest PCE, specifically 6.27 %, without pre- or post-treatments. The promising PCEs achieved from these easily synthesized acene-modified small molecules suggested that acene-modified small molecules can be useful materials in OPVs.

Isoindigo-based polymer photovoltaics: modifying polymer molecular structures to control the nanostructural packing motif.

Donor molecular structures, and their packing aspects in donor:acceptor active blends, play a crucial role in the photovoltaic performance of polymer solar cells. We systematically investigated a series of isoindigo-based donor polymers within the framework of a three-dimensional (3D) crystalline motif by modifying their chemical structures, thereby affecting device performances. Although our isoindigo-based polymer series contained polymers that differed only by their alkyl side chains and/or donating units, they showed quite different nanoscale morphological properties, which resulted in significantly different device efficiencies. Notably, blends of our isoindigo-based donor polymer systems with an acceptor compound, whereby the blends had more intermixed network morphologies and stronger face-on orientations of the polymer crystallites, provided better-performing photovoltaic devices. This behavior was analyzed using atomic force microscopy (AFM) and two-dimensional grazing incidence wide angle X-ray diffraction (2D-GIWAXD). To the best of our knowledge, no correlation has been reported previously between 3D nano-structural donor crystallites and device performances, particularly for isoindigo-based polymer systems.

Optimization of Al2O3/TiO2 nanolaminate thin films prepared with different oxide ratios, for use in organic light-emitting diode encapsulation, via plasma-enhanced atomic layer deposition.

Encapsulation is essential for protecting the air-sensitive components of organic light-emitting diodes (OLEDs), such as the active layers and cathode electrodes. Thin film encapsulation approaches based on an oxide layer are suitable for flexible electronics, including OLEDs, because they provide mechanical flexibility, the layers are thin, and they are easy to prepare. This study examined the effects of the oxide ratio on the water permeation barrier properties of Al2O3/TiO2 nanolaminate films prepared by plasma-enhanced atomic layer deposition. We found that the Al2O3/TiO2 nanolaminate film exhibited optimal properties for a 1 : 1 atomic ratio of Al2O3/TiO2 with the lowest water vapor transmission rate of 9.16 × 10(-5) g m(-2) day(-1) at 60 °C and 90% RH. OLED devices that incorporated Al2O3/TiO2 nanolaminate films prepared with a 1 : 1 atomic ratio showed the longest shelf-life, in excess of 2000 hours under 60 °C and 90% RH conditions, without forming dark spots or displaying edge shrinkage.

Fluorinated polymer-grafted organic dielectrics for organic field-effect transistors with low-voltage and electrical stability.

The electrical stabilities of low-voltage organic field-effect transistors (OFETs) were improved by applying graftable fluorinated polymer (gPFS) layers onto poly(4-vinyl phenol)-based cross-linked dielectrics (cPVP). As a result, a smooth and hydrophobic surface was formed, and the dielectric film displayed a low-leakage current density. The chemisorbed gPFS groups enabled the solution processing of an overlying 5,11-bis(triethylsilylethynyl)anthradithiophene semiconductor, which formed favorable terrace-like crystalline structures after solvent annealing. The top-contact OFETs showed superior operational stability compared to cPVP-based OFETs. Hysteresis was negligible, and the off-current of the transfer curve was one order of magnitude lower than that obtained from cPVP-based OFETs. The threshold voltage shift measured after a sustained gate bias stress for 1 h decreased significantly after introduction of the hydrophobic gPFS treatment; the energetic barrier to creating charge trapping sites increased, and the trap distribution narrowed, as supported by the stretched exponential function model.

Solution-processed n-type fullerene field-effect transistors prepared using CVD-grown graphene electrodes: improving performance with thermal annealing.

Solution-processed organic field effect transistors (OFETs), which are amenable to facile large-area processing methods, have generated significant interest as key elements for use in all-organic electronic applications aimed at realizing low-cost, lightweight, and flexible devices. The low performance levels of n-type solution-processed bottom-contact OFETs unfortunately continue to pose a barrier to their commercialization. In this study, we introduced a combination of CVD-grown graphene source/drain (S/D) electrodes and fullerene (C60) in a solution-processable n-type semiconductor toward the fabrication of n-type bottom-contact OFETs. The C60 coating in the channel region was achieved by modifying the surface of the oxide gate dielectric layer with a phenyl group-terminated self-assembled monolayer (SAM). The graphene and phenyl group in the SAMs induced π-π interactions with C60, which facilitated the formation of a C60 coating. We also investigated the effects of thermal annealing on the reorganization properties and field-effect performances of the overlaying solution-processed C60 semiconductors. We found that thermal annealing of the C60 layer on the graphene surface improved the crystallinity of the face-centered cubic (fcc) phase structure, which improved the OFET performance and yielded mobilities of 0.055 cm(2) V(-1) s(-1). This approach enables the realization of solution-processed C60-based FETs using CVD-grown graphene S/D electrodes via inexpensive and solution-process techniques.

Naphtho[2,1-b:3,4-b']dithiophene-based bulk heterojunction solar cells: how molecular structure influences nanoscale morphology and photovoltaic properties.

Organic bulk heterojunction photovoltaic devices based on a series of three naphtho[2,1-b:3,4-b']dithiophene (NDT) derivatives blended with phenyl-C71-butyric acid methyl ester were studied. These three derivatives, which have NDT units with various thiophene-chain lengths, were employed as the donor polymers. The influence of their molecular structures on the correlation between their solar-cell performances and their degree of crystallization was assessed. The grazing-incidence angle X-ray diffraction and atomic force microscopy results showed that the three derivatives exhibit three distinct nanoscale morphologies. We correlated these morphologies with the device physics by determining the J-V characteristics and the hole and electron mobilities of the devices. On the basis of our results, we propose new rules for the design of future generations of NDT-based polymers for use in bulk heterojunction solar cells.

Interface engineering of a highly sensitive solution processed organic photodiode.

We report on tuning of the interfacial properties of a highly sensitive organic photodiode by introducing a buffer layer between the anode and the semiconductor layer. The effects of different buffer layers consisting of a self-assembled monolayer (SAM), PEDOT:PSS, and pentacene on the morphology and crystallinity of the upper-deposited bulk heterojunction semiconductor layer are carefully analyzed combined with electrical analysis. The active layer is controlled to be nearly homogeneous and to have low crystallinity by using a SAM or PEDOT:PSS buffer layers, whereas a highly crystalline morphology is realized by using the pentacene buffer layer. When exposed to light pulses, the external quantum efficiency and thus the photocurrent are slightly higher for the PEDOT:PSS-based photodiode; however the dark current is the lowest for the pentacene-based photodiode. We discuss the origin of the high sensitivity (a detectivity of 1.3 × 10(12) Jones and a linear dynamic range of 95 dB) of the pentacene-based photodiode, particularly in terms of the morphology-driven low dark current.

The effect of branched versus linear alkyl side chains on the bulk heterojunction photovoltaic performance of small molecules containing both benzodithiophene and thienopyrroledione.

To evaluate the effect of side chain characteristics on the photovoltaic performance of small molecules containing both benzodithiophene (BDT) and thienopyrroledione (TPD), we designed and synthesized two such molecules, one containing a branched 2-ethylhexyl (2EH) side chain on the BDT unit (BDTEH-TTPD) and the other containing a linear n-octyl (C8) side chain on the BDT unit (BDTO-TTP). The optical and electrochemical properties and crystalline structures of these molecules were examined. Compared to BDTO-TTPD, BDTEH-TTPD, showed stronger light absorption, longer-range ordering and shorter π-π stacking distances between backbones. As a result, the power conversion efficiency of a bulk heterojunction solar cell based on BDTEH-TTPD (2.40%) was substantially higher than that of the BDTO-TTPD device (1.12%).

Synthesis and transistor properties of asymmetric oligothiophenes: relationship between molecular structure and device performance.

A series of three thiophene-naphthalene-based asymmetric oligomers-5-decyl-2,2':5',2'':5'',2'''-quaterthiophene (DtT), 5-decyl-5''-(naphthalen-2-yl)-2,2':5',2''-terthiophene (D3TN), and 5-(4-decylphenyl)-5'-(naphthalen-2-yl)-2,2'-bithiophene (DP2TN)-was synthesized by Suzuki cross-coupling reactions. The long alkyl side chains improved both the solubility of the oligomers in solvents and their tendency to self-assemble. UV/Vis absorption measurements suggested that DtT, D3TN, and DP2TN form H-type aggregates with a face-to-face packing structure. In addition, the three oligomers were found to adopt vertically aligned crystalline structures in films deposited on substrates, as revealed by grazing-incidence wide-angle X-ray scattering. These oligomers were used as the active layers of p-type organic field-effect transistors, and the resulting devices showed field-effect mobilities of 3.3×10(-3)  cm(2) V(-1) s(-1) for DtT, 1.6×10(-2)  cm(2) V(-1) s(-1) for D3TN, and 3.7×10(-2)  cm(2) V(-1) s(-1) for DP2TN. The differences in transistor performances were attributed to the degree of π overlap and the morphological differences determined by the molecular structures.

Enhanced performance of organic light emitting device by incorporating 4,4-bis(2,2-diphenylvinyl)-1,1-biphenyl as an efficient hole-injection nano-layer.

Here we reported that 4,4-bis(2,2-diphenylvinyl)-1,1-biphenyl (DPVBi), known as blue emitting host material, could effectively manipulate the Schottky energy barrier between the indium tin oxide (ITO) and the emitting layer and thus significantly enhanced hole injection property. As a result, we could greatly improve the current and luminance efficiencies of organic light emitting diodes (OLEDs) as well as their stability. We attributed the enhanced performance of hole injection layer (HIL)-modified OLEDs to the lowered hole injection barrier. By analyzing the J-V characteristics of hole only devices as a function of temperature, we could show that the interfacial energy barrier between ITO and emitting layer was reduced by more than 0.2 eV by insertion of DPVBi HIL.

Symmetric long alkyl chain end-capped anthracene derivatives for solution-processed organic thin-film transistors.

Three new anthracene derivatives, 2,6-bis(4-decylphenyl)anthracene (DDPAnt), 2-decyl-5-(2-(5-decylthiophen-2-yl)anthracen-6-yl)thiophene (DDTAnt), and 2,6-bis(4-decyloxy phenyl) anthracene (DDPXAnt) were synthesized by Suzuki cross-coupling reaction. The obtained oligomers were characterized by 1H NMR, FT-IR, Mass, UV-visible spectroscopy, cyclovotammetry, differencial scanning calorimetry, and thermogravimetric analysis. The thermal studies show that these oligomers are stable up to 400 degrees C. The solution processed OTFTs were fabricated using synthesized oligomers by spin-coating and drop casting processes on Si/SiO2. OTFTs based on DDPAnt showed the mobility of 7.6 x 10(-3) cm2/Vs and on/off ratio of 10(5).

Strategy for Selective Printing of Gate Insulators Customized for Practical Application in Organic Integrated Devices.

Direct drawing techniques have contributed to the ease of patterning soft electronic materials, which are the building blocks of analog and digital integrated circuits. In parallel with the printing of semiconductors and electrodes, selective deposition of gate insulators (GI) is an equally important factor in simplifying the fabrication of integrated devices, such as NAND and NOR gates, and memory devices. This study demonstrates the fabrication of six types of printed GI layers (high/low-k polymer and organic-inorganic hybrid material), which are utilized as GIs in organic field-effect transistors (OFETs), using the electrostatic-force-assisted dispensing printing technique. The selective printing of GIs on the gate electrodes enables us to develop practical integrated devices that go beyond unit OFET devices, exhibiting robust switching performances, non-destructive operations, and high gain values. Moreover, the flexible integrated devices fabricated using this technique exhibit excellent operational behavior. Therefore, this facile fabrication technique can pave a new path for the production of practical integrated device arrays for next-generation devices.

Electrohydrodynamic-Jet-Printed Cinnamate-Fluorinated Cross-Linked Polymeric Dielectrics for Flexible and Electrically Stable Operating Organic Thin-Film Transistors and Integrated Devices.

Herein, printable polymer series containing different portions of cinnamate and perfluorinated phenyl functionalities, namely, polyperfluorostyrene-co-poly(vinylbenzyl cinnamates) (PFS-co-PVBCi (x:y)) copolymers, were synthesized and applied as gate dielectrics for organic thin-film transistors (OTFTs). The polymeric dielectrics were successfully printed via electrostatic force-assisted dispensing mode of electrohydrodynamic jet printing. The dielectric characteristics of the printed polymers, such as surface energy, dielectric constant, leakage current, atomic depth profiles, and deposited semiconducting layer characteristics, were clearly identified. In particular, the difference in driving stability of OTFTs according to the type of polymer was analyzed in detail and a possible mechanism was proposed. Results suggested that PFS-co-PVBCi (3:7) led to optimized consequences, yielding an almost negligible Vth shift under continuous bias stress. Through this, we successfully implemented flexible OTFT and logic devices using printed PFS-co-PVBCi (3:7) dielectrics with stable operation properties. Therefore, we believe that this study will facilitate the printing and synthesis of polymer dielectrics to produce printed and flexible OTFTs.

Mass-Synthesized Solution-Processable Polyimide Gate Dielectrics for Electrically Stable Operating OFETs and Integrated Circuits.

Polyimides (PIs) are widely utilized polymeric materials for high-temperature plastics, adhesives, dielectrics, nonlinear optical materials, flexible hard-coating films, and substrates for flexible electronics. PIs can be facilely mass-produced through factory methods, so the industrial application value is limitless. Herein, we synthesized a typical poly(amic acid) (PAA) precursor-based solution through an industrialized reactor for mass production and applied the prepared solution to form thin films of PI using thermal imidization. The deposited PI thin films were successfully applied as gate dielectrics for organic field-effect transistors (OFETs). The PI layers showed suitable characteristics for dielectrics, such as a smooth surface, low leakage current density, uniform dielectric constant (k) values regardless of frequency, and compatibility with organic semiconductors. Utilizing this PI layer, we were able to fabricate electrically stable operated OFETs, which exhibited a threshold voltage shift lower than 1 V under bias-stress conditions and a field-effect mobility of 4.29 cm2 V-1 s-1. Moreover, integrated logic gates were manufactured using these well-operated OFETs and displayed suitable operation behavior.

Direct Printing of Asymmetric Electrodes for Improving Charge Injection/Extraction in Organic Electronics.

Engineering the energy levels of organic conducting materials can be useful for developing high-performance organic field-effect transistors (OFETs), whose electrodes must be well controlled to facilitate easy charge carrier transport from the source to drain through an active channel. However, symmetric source and drain electrodes that have the same energy levels are inevitably unfavorable for either charge injection or charge extraction. In this study, asymmetric source and drain electrodes are simply prepared using the electrohydrodynamic (EHD)-jet printing technique after the careful work function engineering of organic conducting material composites. Two types of additives effectively tune the energy levels of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate-based composites. These solutions are alternately patterned using the EHD-jet printing process, where the use of an electric field makes fine jet control that enables to directly print asymmetric electrodes. The asymmetric combination of EHD-printed electrodes helps in obtaining advanced charge transport properties in p-type and n-type OFETs, as well as their organic complementary inverters. This strategy is believed to provide useful guidelines for the facile patterning of asymmetric electrodes, enabling the desirable properties of charge injection and extraction to be achieved in organic electronic devices.

Solution-processed flexible ZnO transparent thin-film transistors with a polymer gate dielectric fabricated by microwave heating.

We report the development of solution-processed zinc oxide (ZnO) transparent thin-film transistors (TFTs) with a poly(2-hydroxyethyl methacrylate) (PHEMA) gate dielectric on a plastic substrate. The ZnO nanorod film active layer, prepared by microwave heating, showed a highly uniform and densely packed array of large crystal size (58 nm) in the [002] direction of ZnO nanorods on the plasma-treated PHEMA. The flexible ZnO TFTs with the plasma-treated PHEMA gate dielectric exhibited an electron mobility of 1.1 cm(2) V(-1) s(-1), which was higher by a factor of approximately 8.5 than that of ZnO TFTs based on the bare PHEMA gate dielectric.

Enhanced chemical and physical properties of PEDOT doped with anionic polyelectrolytes prepared from acrylic derivatives and application to nanogenerators.

Acrylic monomers, 4-hydroxybutyl acrylate (HBA) and 2-carboxyethyl acrylate (CEA), were each co-polymerized with styrene sulfonate in 10 mol% ratio to synthesize two types of anionic polyelectrolytes, P(SS-co-HBA) and P(SS-co-CEA), respectively. Through oxidative polymerization, two types of PEDOT composites (PEDOT:P(SS-co-HBA) and PEDOT:P(SS-co-CEA)) were synthesized, to which the anionic templates were applied as dopants. The composites were similar to PEDOT:PSS; however, crosslinking occurred with an increase in annealing temperature after film casting, which increased the electrical conductivity and hydrophobicity. The composites were applied as electrodes to PVDF-based piezoelectric nanogenerators (PNGs) having an electrode/PVDF/electrode structure. The output voltage, current, and maximum output power of PNG-2D(60) (PEDOT:P(SS-co-HBA)) annealed at a mild temperature (60 °C) were 4.12 V, 817.3 nA, and 847.5 nW, respectively, while those of PNG-3D(60) (PEDOT:P(SS-co-CEA)) annealed at 60 °C were 3.75 V, 756.5 nA, and 716.9 nW, respectively. Thus, the composites showed 13.4% and 11.3% improvements in the maximum output power compared with that of PNG-2D & 3D(RT) dried at room temperature, respectively. These results indicated 27.4% and 7.8% improvements, respectively, compared with PNG-1D(60) in which PEDOT:PSS without any crosslinking effect was applied. The PNGs demonstrated high potential as power sources owing to their sensitivity and excellent charging voltage performance for a 1 µF capacitor.

Facile and Microcontrolled Blade Coating of Organic Semiconductor Blends for Uniaxial Crystal Alignment and Reliable Flexible Organic Field-Effect Transistors.

The ability to fabricate uniform and high-quality patterns of organic semiconductors using a simple method is necessary to realize high-performance and reliable organic field-effect transistors (OFETs) for practical applications. Here, we report the facile fabrication of chemically patterned substrates in order to provide solvent wetting/dewetting regions and grow patterned crystals during blade coating of a small-molecule semiconductor/insulating polymer blend solution. Polyurethane acrylate is selected as the solvent dewetting material, not only because of its hydrophobicity but also because its patterns are easily produced by selective UV irradiation onto precursor films. 6,13-Bis(triisopropylsilylethynyl)pentacene (TIPS-PEN) crystal patterns are grown on the line-shaped wetting regions of the patterned film, and the crystallinity of TIPS-PEN and alignment of molecules are found using various crystal analysis tools depending on the pattern widths. The smallest width of 5 µm yielded an OFET showing the highest field-effect mobility value of 1.63 cm2/(V·s), which is much higher than the value of the OFET based on the unpatterned TIPS-PEN crystal. Notably, we demonstrate flexible and low-voltage-operating OFETs for practical use of the patterned crystals, and the OFETs show highly stable operation under sustained gate bias stress thanks to the patterned crystals.

Side chain engineering in DTBDT-based small molecules for efficient organic photovoltaics.

A new small-molecule donor with a dithieno[2,3-d:2',3'-d']-benzo[1,2-b:4,5-b']-dithiophene (DTBDT) core and both alkyl and alkylthio substituents is designed and synthesized to improve the miscibility between DTBDT-based small molecules and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). The alkyl substituent on the 4-position and the alkylthio substituent on the 5-position of the substituted thiophene are expected to improve intermolecular interactions and prevent severe aggregation of the small molecules. The new small molecule, DTBDT-S-C8-TTR, exhibits a homogenous blend morphology with small domains and edge-on-oriented crystalline structures in blends with PC71BM, and give a maximum power conversion efficiency (PCE) of 8.43%. To recover the crystallinity of the DTBDT-S-C8-TTR small molecules weakened after being blended with PC71BM, a solvent vapor annealing (SVA) treatment is performed. The SVA-treated blend films reveal well-developed crystalline domains with interconnected fibrillar structures. This blend morphology allows efficient charge carrier transport in blends and leads to increased PCEs. The maximum PCE of 9.18% achieved using DTBDT-S-C8-TTR suggests that substituting both alkylthio and alkyl groups into DTBDT can yield small-molecule-based organic photovoltaics (OPVs) displaying improved photovoltaic performances.